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Hydrodesulfurization unit for natural gas condensate: Simulation based on

Aspen Plus software

Article  in  Journal of Thermal Analysis and Calorimetry · February 2019

DOI: 10.1007/s10973-018-7512-4

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Journal of Thermal Analysis and Calorimetry
https://doi.org/10.1007/s10973-018-7512-4(0123456789().,-volV)(0123456789().,-volV)

Hydrodesulfurization unit for natural gas condensate

Simulation based on Aspen Plus software

Javad Ahmadpour1 • Mahyar Ahmadi1 • Amirhossein Javdani1

Received: 23 February 2018 / Accepted: 28 June 2018

Ó Akadémiai Kiadó, Budapest, Hungary 2018

Abstract
Nowadays, most of the world’s energy consumption is from fossil fuels. One of these fossil fuels is natural gas condensate
which consists of various hydrocarbon components and could be used as the main fuel resource. However, these con-
densates contain sulfur contents (0.048 mass%) such as hydrogen sulfide, thiols (mercaptan), and aromatics, which are
known as environmental pollutants. Hence, these sour hydrocarbon resources need to be purified to reduce the sulfur
content. This study concerns the desulfurization of the natural gas condensate of South Pars field of Iran along with the
elimination of disulfide oils of South Pars refinery, through hydrodesulfurization approach, which is simulated using Aspen
Plus software. To reduce operating costs, unused hydrogen in outlet stream is recovered by the amine treatment. Purified
condensates contain ‘‘petroleum cuts’’ which are classified by their boiling point ranges. These petroleum cuts from
distillation unit are composed of butane, light naphtha, heavy naphtha, kerosene, and gasoil. The aim of this study is to
reduce the sulfur content of these hydrocarbon cuts to less than 10 ppmw. The simulation results showed that the final
products of distillation column were sulfur free (with sulfur content less than 1 ppmw). In this article, one optimization
problem is formulated and solved using Aspen Plus software, to obtain the optimal stripper reflux ratio and feed stage. The
objective function chosen in our optimization study is the minimization of the sulfur mass fraction at the bottom of stripper.
To reduce the energy consumption, the effect of the reflux ratio on the reboiler and condenser duty was also studied by
performing a sensitivity analysis. It was found that in the reflux ratio range from 3 up to 3.5 not only the mass fraction of
sulfur at the bottom of the stripper was reduced but also the reboiler and condenser duty was minimized.

Keywords Gas condensates  Disulfide oils  Sulfur content  Hydrodesulfurization  Aspen Plus

Introduction hydrogen sulfide, is sent to a gas treatment and the liquid

As the demand for consumed energy is growing in the
world, new fuel resources are getting attention. Natural gas
condensates which contain complex mixtures of hydro-
carbon components could be considered as one main fuel
resource. Natural gas is typically separated into a gaseous
fraction and a liquid fraction using a separator vessel. The
gaseous fraction leaving the separator, which may contain
the impurities such as mercury, carbon dioxide and
& Javad Ahmadpour
j_ahmadpour@yahoo.com
1
Chemical Engineering Department, Babol Noshirvani
University of Technology, P.O. Box 484, Babol 4714871167,
Iran
fraction called ‘‘gas condensate’’ which contains sulfur
contents, is fed into a reactor containing a catalyst along
with a stream of hydrogen gas. The product leaving the
reactor contains a mixture of hydrogen, hydrogen sulfide,
and natural gas condensate having a reduced amount of
sulfur [1].
Nowadays, sulfur removal in diesel fuels is strongly
desirable for environmental and technical reasons such as
equipment failure, corrosibility in oils and lubricants and
poisonous emissions such as SO2 and H2S when the fuel is
burned [2, 3]. Therefore, the permissible sulfur content in
many fuels has been limited from 500 ppm to 15 ppm ,
which was the limitation given in 2006, by U.S. Environ-
mental Protection Agency. A wide range of different sulfur
compounds are present in petroleum feedstocks. So,

123

according to the type of sulfur-containing compounds, the
processing conditions are different. For example, depending
on sulfuric compound type, two kinds of trickle-bed reactors
for heavier streams and gas-phase fixed-bed reactors for
lighter ones are usually used in hydrotreating process.
Generally, there are two main types of the sulfuric com-
pound in fossil fuels, aromatics and non-aromatic. The first
group includes sulfides, disulfides, and mercaptans (thiols)
and the second one includes thiophenes, benzothiophenes,
dibenzothiophenes, and benzonaphthothiophenes [4, 5].
The reduction in sulfur content, aromatic content and
metal compounds is accomplished by the hydrodesulfur-
ization process (HDS) [2]. HDS is a process that can be
used to remove ‘‘objectionable elements’’ such as sulfur
from products or feedstocks by reacting them with hydro-
gen. HDS reactions are normally performed below 427 °C
to minimize cracking and in the presence of the metal-
oxide catalyst, the hydrogen reacts with the oil to produce
hydrogen sulfide. The oil feed combined with the hydro-
gen-rich gas enters the top of the reactor and after the
mixture passes through the reactor, the products leave the
reactor along with an oil–hydrogen stream. Finally, the oil
is stripped of any remaining hydrogen sulfide in a stripper
[6]. Since the results of HDS process depends on feed
composition, types of sulfur content, operating conditions
and the catalysts employed, different operating conditions,
temperature, and reactor space–time can be employed to
modify the process. However, it has been observed that
coke formation on the catalyst and consequently catalyst
deactivation occur because of high reaction temperature
and efficiency is reduced because of high space–time [3, 4].
Gas condensate of South Pars field is currently sent to
refineries to produce fuel cuts, but gas condensate with
high sulfur content can seriously cause equipment failure
due to corrosion and increase the cost of the process. In
addition to high sulfur content, sour petroleum cuts can
cause major problems in refinery process equipment.
Hence, a distillation system is required to obtain clean cuts
[5]. Moreover, there is an environmental issue which is
related to the production of disulfide oil (DSO) in South
Pars refinery. The substance is a combination of dialkyl
disulfides and trisulfides which is formed in mercaptan
removal process in refineries. DSOs do not have any
commercial or industrial value and its combustion results
in the formation of sulfur dioxide and carbonyl compounds.
Fortunately, in HDS process, DSOs easily convert to
alkanes and hydrogen sulfide [7].
Recently, some studies have been investigating HDS
plant and simulation and modeling them using Aspen
HYSYS [5, 8–10], computer-aided modeling [11] and
artificial neural network [12].Ordouei [9] designed a
hydrogenation plant using Aspen HYSYS to produce and
123
J. Ahmadpour et al.
purify over 98,000,000 kg per annum of different products;
e.g. Benzene, Toluene, Iso-octane etc. with fairly high
purity from the initial components. In another study,
Bilal et al. [8] simulated an HDS unit using Aspen HYSYS
with the aim of removing impurities such as sulfur, nitro-
gen, and oxygen from raw kerosene. Kadijani et al. [5]
simulated an HDS unit using Aspen HYSYS and obtained a
sulfur content less than 30 ppmw in all products. In a
different approach, Jimenez et al. [11] employed computer-
aided modeling to predict the quality of products during the
hydrodesulfurization of a vacuum gas oil (VGO). More-
over, Arce-Medina et al. [12] developed three neural net-
work models for HDS process to predict the sulfur removal
from naphtha.
Since without simulation, modeling and design of large
plants like HDS would be expensive and time-consuming,
highly accurate results are needed in an effective simulation.
To improve the accuracy of the simulation, Aspen Plus
software was employed in this paper. To the best of our
knowledge, this is the first simulation and modeling of HDS
plant with Aspen Plus. The present study investigates an
HDS process for the removal of sulfur from a natural gas
condensate and minimizes the risk of harm to expensive
processing equipment by providing a successful simulation
for the removal of sulfur from natural gas condensates. Also,
we added a stream of DSOs to gas condensate which is sent to
HDS unit as a feed, to simulate a new HDS unit which treats
gas condensate and totally removes DSOs from South Pars
refinery. After HDS process, clean petroleum cuts like
butane, light naphtha, heavy naphtha, kerosene, and gasoil
are obtained from a fractional distillation unit. Moreover, a
single-objective optimization is formulated and solved using
Aspen Plus software to obtain the optimal operating condi-
tions that minimize the sulfur mass fraction at the bottom of
stripper. Finally, a sensitivity analysis was carried out to
investigate the effect of the reflux ratio on the reboiler and
condenser duty.
Feed stream properties
The effectiveness of HDS process depends on general feed
composition. The feed stream of HDS unit is the gas
condensate flow combined with a stream of DSOs [4, 5].
The characteristics of gas condensate mixture, which is
used in this study, based on true boiling points (TBP) at
0 °C and 760 mmHg is shown in Table 1. From given data
from Kadijani et al. [5] simulation, molecular weight and
mass density for gas condensate were assumed to be 120
and 756 kg m-3, respectively. Mass fraction of non-sul-
furic and sulfuric components of gas condensate in gas
condensate flow are shown in Tables 2 and 3. Moreover,
two sulfuric compounds of the DSO are used in this study
Hydrodesulfurization unit for natural gas condensate

Table 1 The characteristics of Methodology

Volume/% TBP/°C
gas condensate mixture based
on true boiling points [5] 5.18 15 Aspen Plus is a very powerful process simulator which is
11.49 36.1 used for modeling chemical processes [13]. To simulate the
53.24 150 HDS unit with a distillation section to desulfurize gas
63.09 175 condensate and DSO stream, Aspen Plus software package
73.41 215 was used. In the first step of simulation with Aspen Plus,
81.76 250 components of streams must be defined and then the
87.01 275 thermodynamic model should be specified. Chao-Seader
95.81 350 thermodynamic model which is most adapted to HDS
100 360 processes and existing components are used in this simu-
lation. Natural gas condensates that contain complex
mixtures heavier than C6 and TBP assay are applied to
Table 2 The components of gas condensate determine these components specifications. The composi-
Components of gas Mass fraction in the gas tion of other constitutive components of natural gas con-
condensate condensate/mass% densate such as C2 to n-C5 light components with low
Methyl mercaptan 0.002
boiling points is specified by their mass fraction in the feed
stream. Finally, streams of gas condensate and DSO is
Ethyl mercaptan 0.035
created in a simulation environment and process flow
i-Propyl mercaptan 0.025
diagram (PFD) of HDS process is simulated with Aspen
t-Butyl mercaptan 0.001
Plus software as shown in Fig. 1.
n-Propyl mercaptan 0.01
2-Butyl mercaptan 0.0210
Hydrodesulfurization reaction
i-Butyl mercaptan 0.001
n-Butyl mercaptan 0.01
HDS is one of the important catalytic processes in the
Benzothiophenes 0.0056
petroleum industry to remove sulfur content from diesel
Dibenzothiophenes 0.0059
fuel and produce clean fuel [14]. Moreover, transition
metal sulfides (TMS) are unique catalysts for hydrodesul-
Table 3 The non-sulfuric components of gas condensate [5] furization reactions due to their higher activity. Among
Non-sulfuric components of gas condensate Mass fraction/mass% these catalysts, the second and third rows of TMS were
found to be the most active metal-sulfur systems. Ruthe-
Propane 0.3295 nium disulfide has the most intrinsic activity between metal
n-Butane 1.7320 sulfides, but cobalt-molybdenum binary bulk sulfides
i-Butane 0.7798 which have a quite high activity, are used as the main
n-Pentane 0.0212 catalyst of HDS processes [15]. Furthermore, the HDS
i-Pentane 0.1602 catalyst can be formed in different conventional forms such
Water 0.0080 as by depositing a cobalt/molybdenum salt on a solid
support, impregnating the solid with aqueous solutions of
the desired cobalt and molybdenum salts, and then evap-
Table 4 The components in DSO stream [5]
orating the water to dry the catalyst [1].
Sulfur components in DSO Mass Boiling point/ Due to the heavy components in the gas condensate,
stream fraction/mass% °C
HDS reactor should be a trickle-bed reactor. Trickle-bed
Dimethyl disulfide 50 110 reactors are usually used to hydrotreat heavier refinery
Diethyl disulfide 50 154 streams, while gas-phase fixed-bed reactors are commonly
employed to hydrotreating lighter ones [4]. HDS reactor
temperature and pressure are assumed to be 330 °C and
and their boiling points and mass contents in DSO stream 4000 kPa, respectively, in Aspen Plus simulation. Mean-
are shown in Table 4. while, sulfur compounds are converted to hydrogen sul-
Gas condensates stream and a flow of DSOs with the fides in the presence of hydrogen in this reactor. All
volumetric rate of 6360 and 47 m3 per day, respectively, reactions are exothermic and rate of reactions decrease
are mixed and fed to HDS unit [5]. with increasing bed length. Some of the most important

123

TO-FLARE
CMPRSR-2
RECYCLH2
REACHAMI
CMPRSR-1
CV-1
MAKUP-H2 HOT-SEP
FURNACE
TANK HEATEX-1
GAS-CNDS PUMP-1
REACTOR
DS-OIL
Fig. 1 Process flow diagram of HDS unit
reactions during the HDS process may be expressed as
follows:
CH3 SH þ H2 ! CH4 þ H2 S
C2 H5 SH þ H2 ! C2 H6 þ H2 S
C2 H6 S2 þ 3H2 ! 2CH4 þ 2H2 S
C4 H10 S2 þ 3H2 ! 2C2 H6 þ 2H2 S
C8 H6 S þ 3H2 ! C8 H10 þ H2 S
Reaction (1) and (2) are related to mercaptans, reaction (3)
and (4) are, respectively, related to dimethyl disulfide and
diethyl disulfide which exists in DSO stream and reaction (5)
is related to benzothiophenes.
Process description
According to Fig. 1, the liquid feed (mixed stream of gas
condensate and DSO with flow rate of 202,000 kg hr-1) is
pumped up to the required elevated pressure of 4900 kPa
and is joined by a stream of rich hydrogen gas which
consists of a makeup H2 stream with flow rate of
170 kg hr-1 and a recycle hydrogen stream with 61 mol%
purity from amine unit. A compressor is applied to increase
the pressure of recycle hydrogen stream to 4650 kPa.
There is a heat exchanger between the mixed feed and
the outlet stream of the reactor which causes a reduction in
energy consumption in this section of the process. The hot
stream of this heat exchanger is the outlet stream of
the reactor and its cold stream is the mixed feed.
Exchanged heat from hot fluid to cold fluid is 39,601 kW.
The temperature of hot mixed feed reaches 272 °C after
passing through the heat exchanger and then this stream
enters the furnace and exits with a temperature of 330 °C
which is necessary for HDS reactions. All reactions are
defined for Aspen Plus software and the total amount of
heat released in the reactor is 1984 kW.
123
J. Ahmadpour et al.
BUTANE
ABSORBER
LEANAMIN
SEP-3
LNAPHTHA
WATEROFF
WATER
D-COLUMN
H2S
COLD-SEP
HNAPHTHA
STEAM-2
STRPR-1 KEROSENE
STEAM-3
GASOIL
STEAM-1
RESIDUE
Reactor outlet stream is cooled in a heat exchanger to
150 °C and passes a pressure-reducing valve to reach a
ð1Þ pressure of 1650 kpa. Then, this stream is sent to a hot
separator. In this separator, a stream of light components
ð2Þ which consists of 45% mol H2 and 2.04% mol, exists from
ð3Þ top of the separator at 147 °C and enters the cold separator.
The temperature of this stream is cooled to 40 °C before
ð4Þ
entering into the second separator. A stream which is rich
ð5Þ in H2 containing H2S (5.6% mol) exits from the top of the
cold separator and enters the amine treating column. This
column removes H2S from H2 stream using a countercur-
rent amine solution stream in 12 equilibrium stages. Amine
solution stream with a flow rate of 44,165 kg hr-1, con-
tains 72 mass% water, 27 mass% diethanolamine and
0.18 mass% CO2 at the high pressure about 1400 kPa and
the low temperature about 45 °C. Treated H2 exits from the
top of Amine Column and 1% of this stream is sent to flare
and 99% of this stream returns to the unit.
The outlet stream from the bottom of the hot separator
including heavy hydrocarbons is combined with cold sep-
arator bottom stream and enters the stripper for H2S
stripping. The pressure of stripper is 1500 kPa. The outlet
stream from the bottom of a stripper, which contains heavy
hydrocarbons, at a temperature of 225 °C is sent to distil-
lation section to separate into fractions. Stripper column
consists of a partial condenser, reboiler and 20 trays. The
feed stream enters the column at the 5th tray. Reflux ratio is
3 and reboiler heat duty is 16,180 kW.
The pressure of stripper bottom stream is reduced to
400 kPa by a valve to enter the distillation column. The
temperature of stripper bottom stream is raised to 310 °C in
distillation furnace and this stream is sent to the bottom of
the distillation column. The high-pressure steam with a
flowrate of 42 kg per each cubic meter of bottom column
product is injected into the bottom of the distillation col-
umn. The temperature of the top stage of the distillation
column is assumed to be 84 °C and then this flow is cooled
to around 74 °C by the condenser of the distillation
Hydrodesulfurization unit for natural gas condensate

column. The first side stream is drawn from the 26th tray of
the distillation column which contains heavy naphtha and it
is sulfur free. The second side stream of the distillation
column is drawn from the 28th tray and this stream is sent
to kerosene side stripper which has 10 trays. The third side
stream of the distillation column is drawn from the 29th
tray and this stream is sent to the gasoil side stripper which
has 8 trays. Residue products of distillation column which
contains heavy hydrocarbons like butane, light naphtha,
heavy naphtha, kerosene, gasoil, and condensate, leave the
bottom of the distillation column.
The outlet gas stream from the top of the reflux drum
and the outlet liquid flow from the bottom of reflux drum
are mixed and this stream is sent to a separator to remove
the remaining water. Then, this dehydrated hydrocarbon
stream is sent to Debutanizer column which consists of 10
trays, a partial condenser and a reboiler with a reboiler heat
duty of 5467 kW. A stream of butane from the top of this
column and a stream of light naphtha from its bottom are
obtained.
Result and discussion
Aspen Plus software (version 9) is used to simulate the
HDS unit for a mixture of gas condensate and DSO. The
gas condensate is composed of many components with
different boiling points. These different hydrocarbon cuts
are classified by their different boiling point ranges. In this
work, we defined these boiling points ranges based on
refinery products properties (data taken from the Website
of Chevron Company) [5, 16]. The simulation results
showed that five different cuts are obtained from the treated
gas condensate. The mass fraction of sulfur in each product
was less than 1 ppmw. The simulation results are shown in
Table 5.
To better understand this process, two key performance
parameters should be considered. The first parameter is H2
consumption which is defined as the ratio of the volumetric
rate of required hydrogen (at normal condition) to the
volumetric rate of feed. The amount of this parameter is 13
in this process. The other key parameter is ‘‘yield of liquid
product on feed’’, the mass flow rate of the bottom stream
of the stripper is divided by the mass flow rate of feed. The
second parameter is equal to 95 in this simulation.
The HDS process basically consists of three sections
namely; reaction section, stripping section and the distil-
lation section. Due to the complex dependencies of strip-
ping section on mass fraction of sulfur in the distillation
feed, optimization studies are required to be carried out to
obtain the optimal process conditions to achieve a mini-
mum mass fraction of sulfur at the bottom of stripper.
Outlet mass fraction of sulfur is considered as an objective
function. The main process variables which affect objective
function are stripper feed stage (FS) and reflux ratio (RR)
and, hence, are taken as decision variables. The optimiza-
tion problem is formulated by taking one objective func-
tion, namely, ‘‘outlet mass fraction of sulfur’’, and two
decision variables, namely, FS and RR. This is mathe-
matically described by
Min f ðFS; RR) ¼ outlet mass fraction of sulfur
Bounds:
2  FS  21
0:1  RR  7
These chosen operating conditions are in the range of
the industrially operating conditions. This optimization
problem is solved using optimization tool available in
Aspen Plus software. Optimal values of process variables
and corresponding objective function values obtained for
the problem are presented in Table 6.

Table 5 Process parameters and state conditions for the streams

Streams Flow rate/ Pressure/ Temperature/°C Sulfur/mass% Hydrogen/ H2O/mass% Light Condensate/mass%
kg hr-1 kPa mass% gas/mass%

Gas condensate 200,000 101.325 27 0.048 0 0.01 3 97

DSO 2000 641.325 50 60 0 0 0 0
Quench H2 16,703 4650 161 6 9.3 1 64.3 25.4
1:73  10
Butane 3135 181 17 7 0 0 98.6 1.4
9:4  10
Light naphtha 25,665 281 70 4:6  106 0 0 1.45 98.55
Heavy naphtha 83,520 378 153 6 0 0 0.09 99.91
3:08  10
Kerosene 40,890 379 182 7  109 0 0 0 100
Gasoil 35,000 379 234 1:83  1010 0 0 0 100

123
 J. Ahmadpour et al.

Table 6 Optimal values of

Process variables Objective function
process variables and objective
function Variable name Initial value Optimal value Initial value/ppm Final value/ppm

Feed stage (FS) 5 2 0.01925 0.01917

Reflux ratio (RR) 3 3 0.01925 0.01925

18000 0
Sensitivity results curve
17500
– 500
17000
– 1000
16500 REBOIL KW
CONDENS KW

– 1500 CONDENS KW
REBOIL KW

16000
15500 – 2000

15000 – 2500
14500
– 3000
14000
– 3500
13500
13000 – 4000

12500 – 4500
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
VARY 1 STRPR–1 COL–SPEC MOLE–RR

Fig. 2 The effect of reflux ratio on reboiler duty and condenser duty

It is clear from Table 6 and results of optimization
problem that there is an optimum feed stage (which exists
between lower and upper bounds) and an optimum reflux
ratio (which exists between lower and upper bounds) which
favors low outlet mass fraction of sulfur. It should be
pointed out that the initial value of reflux ratio that was
used in the simulation was equal to the optimal value.
Moreover, there is an optimal reflux ratio that minimizes
the energy consumption in reboiler and condenser. The
energy consumptions during stripping process can have a
strong impact on overall profitability. Therefore, we carried
out a sensitivity analysis to find optimum reflux ratio that
minimizes the reboiler and condenser duty. The sensitivity
analysis result is shown in Fig. 2.
The effect of reboiler duty and condenser duty was seen
by varying the reflux ratio in the range of 0.5–7. It was
found that reboiler and condenser duty was optimum at
reflux ratio range from 3 up to 3.5 which matched with the
reflux ratio mentioned in the optimization problem.
Conclusions and outlook
To reduce environmental pollutants of sulfur-containing
fuels, desulfurization of a natural gas condensate of South
Pars field of Iran and elimination of disulfide oils of South
Pars refinery with hydrodesulfurization (HDS) approach
was simulated using Aspen plus software. This simulation
consists of desulfurization and distillation. In the simulated
HDS unit, gas condensate is purified and DSO which is
considered as an environmental pollution is totally
removed. The simulation results showed that the mass
fraction of sulfur in the five cuts involving butane, light
naphtha, heavy naphtha, kerosene, and gasoil which are
obtained from gas condensate was less than 1 ppmw.
Moreover, to obtain the highest performance, an opti-
mization carried out by varying different operation condi-
tions like stripper feed stage (FS) and reflux ratio (RR). To
reduce the energy consumption, the effect of the reflux
ratio on the reboiler and condenser duty was also studied
by performing a sensitivity analysis.
This work is in fact, a conceptual design as a part of the
basic design. More simulation works should be done in
future to provide a detailed design of HDS plant such as
decreasing the energy consumption of the plant, developing
a control system for this plant and performing a dynamic
simulation.
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